Process for preparing alkyl substituted para-carboalkoxy cyclohexanones

ABSTRACT

Described are para-carboalkoxy cyclohexanones defined according to the structure: ##STR1## wherein R 1  represents hydrogen or C 1  -C 7  alkyl and R 2  represents methyl or ethyl and uses thereof in augmenting or enhancing the aroma of consumable materials including foodstuffs, chewing gums, toothpastes, medicinal products, chewing tobaccos, perfume compositions, colognes and perfumed articles (e.g., solid or liquid anionic, cationic, nonionic or zwitterionic detergents, cosmetic compositions, fabric softener compositions, fabric softener articles, hair preparations and perfumed polymers. The compounds defined according to the structure: ##STR2## wherein R 1  &#39; represents C 4  -C 7  alkyl and R 2  represents methyl or ethyl are novel compounds.

This is a divisional of application Ser. No. 747,551, filed 6/21/85,which, in turn, is a divisional of application for U.S. Patent, Ser. No.563,801 filed on 12/21/83, now U.S. Pat. No. 4,537,704 issued on Aug.27, 1985.

BACKGROUND OF THE INVENTION

This invention relates to para-carboalkoxy cyclohexanones definedaccording to the structure: ##STR3## wherein R₁ represents hydrogen orC₁ -C₇ alkyl and R₂ represents methyl or ethyl and uses thereof inaugmenting or enhancing the aroma or taste of consumable materials.

There has been considerable work performed relating to substances whichcan be used to impart (modify, augment or enhance) flavors to (or in)foodstuffs. These substances are used to diminish the use of naturalmaterials, some of which may be in short supply and to provide moreuniform properties in the finished product.

Nutty, raspberry, kernel-like, tart, unripened lime, bitter, lemony,green, caramel-like, maple sugar-like, maple/hazel-nut, and intensecocoa and coffee, fresh almond aroma and taste with blueberry-like andcoffee nuances are particularly desirable for uses in many foodstuffflavors, particularly in raspberry ice cream flavors, cooked raspberrypies, blueberry pies and the like.

Fruity, woody, strawberry-like, raspberry-like, green, fresh floral,jasmine-like, lemony, burnt maple, maple/nutty, meaty, cocoa, coffee andvalerian-like aromas with woody, ionone-like, sweet raspberry-like,licorice-like, jasmine-like, citrusy, lemon, and toasted almondundertones are particularly desirable in augmenting or enhancing thearoma of perfume compositions, colognes and perfumed articles (e.g.,solid or liquid anionic, cationic, nonionic or zwitterionic detergents,fabric softener compositions, fabric softener articles, hairpreparations, cosmetic powders and perfumed polymers.

Perfume uses of carboalkoxy cyclohexanones and carboalkoxycyclopentenones are well known in the prior art. Thus, U.S. Pat. No.4,310,701 issued on Jan. 12, 1982 discloses compounds defined accordingto the generic structure: ##STR4## wherein R₁₃ represents C₁ -C₄ alkyland R₁₂ represents C₁ -C₃ alkyl. United Kingdom Patent Specification907,431 published on Oct. 3, 1962 discloses compounds defined accordingto the generic structure: ##STR5## as being useful in perfumery (whereinR₁₁ represents lower alkyl and R₁₀ represents lower alkyl).

Para-carboalkoxy cyclohexanones substituted at a position alpha to theketo moiety are also well known in the prior art. Thus, the compounddefined according to the structure: ##STR6## has been indicated to havebeen synthesized by Huffman & Sawdaye at Synth. Comm. 11(12) 979-81(1981).

Furthermore, Sengupta, J.Org.Chem. 18, 249-55(1953) abstracted atChem.Abstracts, Vol. 48, 1976 discloses the compound defined accordingto the structure: ##STR7## Neither Huffman & Sawdaye nor Senguptadisclosed their organoleptic uses of these compounds.

Nothing in the prior art discloses the use of the paracarboalkoxycyclohexanones defined according to the structure: ##STR8## wherein R₁represents hydrogen or C₁ -C₇ alkyl and R₂ represents methyl or ethyl inaugmenting or enhancing the aroma or taste of consumable materials suchas foodstuffs, perfume compositions, colognes and perfumed articles.Nothing in the prior art discloses the unobvious, unexpected andadvantageous properties of the genus of compounds defined according tothe structure: ##STR9## wherein R₁ ' represents C₄ -C₇ alkyl and R₂represents methyl and ethyl.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is the GLC profile for the reaction product of Example Icontaining the compound having the structure: ##STR10## (conditions:Carbowax column programmed at 225° C. isothermal).

FIG. 2 is the infra-red spectrum for Fraction 4 of the distillationproduct of the reaction product of Example I containing the compoundhaving the structure: ##STR11##

FIG. 3 is the MNR spectrum for Fraction 4 of the distillation product ofthe reaction product of Example I containing the compound having thestructure: ##STR12## (conditions: Field strength: 100 MHz; Solvent:CFCl₃).

FIG. 4 is the NMR spectrum for Fraction 7 of the distillation product ofthe reaction product of Example II containing the compound having thestructure: ##STR13## (conditions: Field strength: 100 MHz; Solvent:CFCl₃).

FIG. 5 is the infra-red spectrum for Fraction 7 of the distillationproduct of the reaction product of Example II containing the compoundhaving the structure: ##STR14##

FIG. 6 is the GLC profile for the reaction product of Example IIIcontaining the compound having the structure: ##STR15##

FIG. 7 is the GLC profile for the reaction product of Example IIIcontaining the compound having the structure: ##STR16##

FIG. 8 is the GLC profile for the reaction product of Example IVcontaining the compound having the structure: ##STR17##

FIG. 9 is the GLC profile for the reaction product of Example IVcontaining the compound having the structure: ##STR18##

FIG. 10 is the NMR spectrum for the reaction product of Example IVcontaining the compound having the structure: ##STR19## (conditions:Field strength: 100 MHz; Solvent: CFCl₃).

FIG. 11 is the NMR spectrum for the reaction product of Example IVcontaining the compound having the structure: ##STR20##

FIG. 12 is the GLC profile for the reaction product of Example Vcontaining the compound having the structure: ##STR21## (conditions:SE-30 column programmed at 180° C. isothermal).

FIG. 13 is the GLC profile for the reaction product of Example Vcontaining the compound having the structure: ##STR22## (Conditions:SE-30 column programmed at 220° C. isothermal).

FIG. 14 is the NMR spectrum for the compound having the structure:##STR23## produced according to Example V. (Conditions: Field strength:100 MHz; Solvent: CFCl₃).

FIG. 15 is the infra-red spectrum for the compound having the structure:##STR24## produced according to Example V.

FIG. 16 is the NMR spectrum for the compound having the structure:##STR25## produced according to Example VI. (Conditions: Field strength:100 MHz; Solvent: CFCl₃).

FIG. 17 is the infra-red spectrum for the compound having the structure:##STR26## produced according to Examle VI. (Conditions: Field strength:100 MHz; Solvent: CFCl₃).

FIG. 18 is the GLC profile for the reaction product of Example VIIcontaining the compound having the structure: ##STR27## (conditions: 10%SE-30 column programmed at 180° C. isothermal).

FIG. 19 is the GLC profile for the reaction product of Example VIIcontaining the compound having the structure: ##STR28## (conditions: 10%SE-30 column programmed at 220° C. isothermal).

FIG. 20 is the NMR spectrum for the reaction product of Example VIIcontaining the compound having the structure: ##STR29## (conditions:Field strength: 100 MHz; Solvent: CFCl₃).

FIG. 21 is the infra-red spectrum for the compound having the structure:##STR30## produced according to Example VII.

FIG. 22 is the GLC profile for the reaction product of Example VIIIcontaining the compound having the structure: ##STR31## (conditions: 10%SE-30 column programmed at 180° C. isothermal).

FIG. 23 is the GLC profile for the reaction product of Example VIIIcontaining the compound having the structure: ##STR32## (conditions: 10%SE-30 column programmed at 220° C. isothermal).

FIG. 24 is the NMR spectrum for the reaction product of Example VIIIcontaining the compound having the structure: ##STR33## (conditions:Field strength: 100 MHz; Solvent: CFCl₃).

FIG. 25 is the infra-red spectrum for the reaction product of ExampleVIII containing the compound having the structure: ##STR34##

FIG. 26 is the GLC profile for the reaction product of Example IXcontaining the compound having the structure: ##STR35## (crude)(conditions: 10% SE-30 column programmed at 180° C. isothermal).

FIG. 27 is the GLC profile for the reaction product of Example IXcontaining the compound having the structure: ##STR36## (conditions: 10%SE-30 column programmed at 220° C. isothermal).

FIG. 28 is the NMR spectrum for the compound having the structure:##STR37## produced according to Example IX. (Conditions: Field strength:100 MHz; Solvent: CFCl₃).

FIG. 29 is the infra-red spectrum for the reaction product of Example IXcontaining the compound having the structure: ##STR38##

FIG. 30 is the NMR spectrum for the reaction product of Example Xcontaining the compound having the structure: ##STR39## (conditions:Field strength: 100 MHz; Solvent: CFCl₃).

FIG. 31 is the infra-red spectrum for the compound having the structure:##STR40## produced according to Example X.

FIG. 32 is the NMR spectrum for the reaction product of Example XI(A)having the structure: ##STR41## (conditions: Field strength: 100 MHz;Solvent: CFCl₃).

FIG. 33 is the infra-red spectrum for the compound having the structure:##STR42## produced according to Example XI(A).

FIG. 34 is the GLC profile for the reaction product of Example XI(B)containing the compound having the structure: ##STR43##

FIG. 35 is the NMR spectrum for the reaction product of Example XI(B)containing the compound having the structure: ##STR44## (conditions:Field strength: 100 MHz; Solvent: CFDl₃).

FIG. 36 is the infra-red spectrum for the compound having the structure:##STR45## produced according to Example XI(B).

FIG. 37 is a partial side elevation and partial sectional view of anapparatus for forming polymer pellets scented with one of the perfumecompositions or perfumery materials of our invention.

FIG. 38 is a section taken on line 38--38 of FIG. 37.

DETAILED DESCRIPTION OF THE DRAWINGS

FIG. 6 is the GLC profile for the reaction product of Example IIIcontaining the compound having the structure: ##STR46## The peakindicated by reference numeral "60" is the peak for the compound havingthe structure: ##STR47##

FIG. 7 is the GLC profile for the reaction product of Example III afterhydrogenation containing the compound having the structure: ##STR48##(conditions: SE-30 column programmed at 220° C. isothermal). The peakindicated by reference numeral "70" is the peak for the compound havingthe structure: ##STR49##

FIG. 8 is the GLC profile for the reaction product of Example IVcontaining the compound having the structure: ##STR50## The peakindicated by reference numeral "80" is the peak for the compound havingthe structure: ##STR51##

FIG. 9 is the GLC profile for the reaction product of Example IV afterthe hydrogenation step. The peak indicated by reference numeral "90" isthe peak for the compound having the structure: ##STR52##

FIG. 12 is the GLC profile for the reaction product of Example Vcontaining the compound having the structure: ##STR53## The peakindicated by reference numeral "121" is the peak for the compound havingthe structure: ##STR54##

FIG. 13 is the GLC profile for the reaction product of Example V afterhydrogenation containing the compound having the structure: ##STR55##The peak indicated by reference numeral "130" is the peak for thecompound having the structure: ##STR56##

FIG. 18 is the GLC profile for the reaction product of Example VIIcontaining the compound having the structure: ##STR57## (conditions: 10%SE-30 column programmed at 180° C. isothermal). The peak indicated byreference numeral "180" is the peak for the compound having thestructure: ##STR58##

FIG. 19 is the GLC profile for the reaction product of Example VII afterhydrogenation containing the compound having the structure: ##STR59##The peak indicated by reference numeral "190" is the peak for thecompound having the structure: ##STR60## (Conditions: 10% SE-30 columnprogrammed at 220° C. isothermal).

FIG. 22 is the GLC profile for the reaction product of Example VIIIcontaining the compound having the structure: ##STR61## (conditions: 10%SE-30 column programmed at 180° C. isothermal). The peak indicated byreference numberal "220" is the peak for the compound having thestructure: ##STR62##

FIG. 23 is the GLC profile for the reaction product of Example VIIIafter hydrogenation containing the compound having the structure:##STR63## (conditions: 10% SE-30 column programmed at 220° C.isothermal). The peak indicated by reference numeral "230" is the peakfor the compound having the structure: ##STR64##

FIG. 26 is the GLC profile for the reaction product of Example IXcontaining the compound having the structure: ##STR65## The peakindicated by reference numeral "260" is the peak for the compound havingthe structure: ##STR66## (conditions: 10% SE-30 column programmed at180° C. isothermal).

FIG. 27 is the GLC profile for the reaction product of Example IX afterhydrogenation containing the compound having the structure: ##STR67##(Conditions: 10 SE-30 column programmed at 220° C. isothermal). The peakindicated by reference numeral "270" is the peak for the compound havingthe structure: ##STR68##

FIG. 34 is the GLC profile for the reaction product of Example XI(B)containing the compound having the structure: ##STR69## The peakindicated by reference numeral "340" is the peak for the compound havingthe structure: ##STR70##

Referring to FIGS. 37 and 38, the apparatus used in producing polymericfragrances containing the para-carboalkoxy cyclohexanones of ourinvention comprises a device for forming scented polyolefin (forexample) pellets which comprises a vat or container 2101 into which amixture of polyolefins such as polyethylene or an aromatic substance orscented material containing or consisting of the para-carboalkoxycyclohexanones of our invention is placed. The container is closed by anair tight lid 228, and clamped to the container by bolts 265. A stirrer273 traverses the lid or cover 228 in air tight manner and is rotated ina suitable manner. A surrounding cyclinder 212 having heating coilswhich are supplied with electric current through cable 224 from arheostat or control 216 is operated to maintain the temperature insidethe container 2101 such that polyethylene or other thermoplastic polymerin the container will be maintained in the molten or liquid state. Ithas been found advantageous to employ a colorless, odorless polymer(e.g. polyethylene) with a viscosity ranging between 180 and 220 Sayboltseconds and having a melting point in the range of 200°-280° F. Theheater 2201 is operated to maintain the upper portion of the container2101 within a temperature range of from 250°-350° F. The bottom portionof the container 218 is heated by means of heating coils 222 heatedthrough a control 2201 connected thereto through a connecting wire 226to maintain the lower portion of the container 218 within thetemperature range of from 250°-350° F.

Thus, polymer (e.g. polyolefin) added to the container 2101 is heatedfrom 10-12 hours whereafter a scent or aroma imparting material whichcontains or consists of at least one of the para-carboalkoxycyclohexanones of our invention is quickly added to the melt. Thematerial must be compatible with the polyolefin and forms a homogeneousliquid melt therewith. The scented material containing or consisting ofone of the para-carboalkoxy cyclohexanones of our invention is of a typefor the particular aroma desired and formulated specifically for thescenting purpose for which the polyolefin will be employed. The heatresisting coils and aromatic materials in some instances in solid orpowdered form may be employed and added to the polyolefin in thecontainer 2101. Generally about 10-30% by weight of scenting material isadded to the polyolefin.

After the scent imparting material containing or consisting of one ofthe para-carboalkoxy cyclohexanones of our invention is added to thecontainer 2101, the mixture is stirred for a few minutes, for example,5-15 minutes and maintained within the temperature ranges indicatedpreviously by the heating coils 212 and 218, respectively. The controls216 and 2201 are connected through cables 224 and 226 to a suitablesupply of electric current for supplying the power for heating purposes.

Thereafter, the valve "V" is opened permitting the mass to flowoutwardly through conduit 232 having a multiplicity of orifices 234adjacent to the lower side thereof. The outer end of the conduit 232 isclosed so that the liquid polymer (e.g. polyolefin) and aroma impartingmixture (containing or consisting of one of the para-carboalkoxycyclohexanones of our invention) will continuously drop through theorifices 234 downwardly from the conduit 232. During this time, thetemperature of the polymer (e.g. polyolefin) and aroma mixturecontaining or consisting of one of the para-carboalkoxy cyclohexanonesof our invention in the container 2101 is accurately controlled so thata temperature in the range of from about 210°-275° F. will exist in theconduit 232. The regulation of the temperature through the control 216and the control 2201 is essential in order to insure temperature balanceto provide for the continuous dropping or dripping of molten polymer(e.g. polyolefin) and scenting material containing or consisting of oneof the para-carboalkoxy cyclohexanones of our invention through theorifices 234 at a rate which will insure the formation of droplets 236which will fall downwardly onto the moving conveyor belt 238 trained torun between conveyor wheels 2401 and 242 beneath the conduit 232.

When the droplets 236 fall onto the conveyor 238, they form pellets 244which harden almost instantaneously and fall off the end of the conveyor238 into a container 259 which is advantageously filled with water orsome other suitable cooling liquid in order to insure the rapid coolingof each of the pellets. The pellets 244 are then collected from thecontainer 259 and utilized in a process as illustrated infra.

A feature of this aspect of the process of our invention is in theprovision for moistening the conveyor belt 238 to insure rapid formationof the solid polymer (e.g. polyolefin) scented pellets 244 withoutsticking to the belt. the belt 238 is advantageously of a material whichwill not normally stick to a melted plastic but the moistening means 248insures a sufficiently cold temperature of the belt surface for theadequate formation of the pellets 244. The moistening means comprises acontainer 259 which is continuously fed with water 252 to maintain alevel 254 for moistening a sponge element 256 which bears against theexterior surface of the belt 238.

THE INVENTION

The instant invention provides a compound defined according to thegeneric structure: ##STR71## wherein R represents hydrogen or C₁ -C₇alkyl; and R₂ represents methyl or ethyl. The compounds are useful inaugmenting or enhancing the aroma and/or taste of consumable materialsincluding foodstuffs, chewing gums, toothpastes, medicinal products,chewing tobaccos, smoking tobaccos, smoking tobacco articles, perfumecompositions, colognes and perfumed articles (including but not limitedto solid or liquid anionic, cationic, nonionic or zwitterionicdetergents, perfumed polymers, fabric softener compositions and fabricsoftener articles, cosmetic powders, hair preparations and the like).

Briefly, our invention contemplates augmenting or enhancing the aroma ortaste of nutty, blueberry, raspberry, citrusy, caramel, maple,hazel-nut, cocoa and coffee flavored foodstuffs. Thus, the compoundsdefined according to the generic structure: ##STR72## wherein R₁represents hydrogen or C₁ -C₇ alkyl and R₂ represents methyl or ethylaugment or enhance nutty, raspberry kernel-like, tarte unripened lime,bitter, lemony, caramel-like, maple sugar-like, maple/hazel-nut, meat,cocoa, coffee and fresh almond aroma and taste nuances in foodstuffs asset forth supra.

Briefly, our invention further contemplates augmenting or enhancing thearoma of perfume compositions, perfumed articles and colognes. Thus, thecompounds defined according to the genus: ##STR73## wherein R₁represents hydrogen or C₁ -C₇ alkyl and R₂ represents methyl or ethylaugment or enhance fruity, woody, strawberry-like, raspberry, green,fresh floral, jasmine-like, lemony, green, burnt maple, maple/nutty,meat/cocoa/coffee and valerian-like aromas with woody, ionone-like,sweet raspberry-like, licorice-like, jasmine-like, citrusy, lemon, andtoasted almond undertones.

The compounds of our invention defined according to the genericstructure: ##STR74## wherein R₁ ' represents C₄ -C₇ alkyl and R₂represents methyl or ethyl are novel compounds.

The compounds of our invention defined according to the genericstructure: ##STR75## wherein R₂ represents methyl or ethyl may beproduced by hydrogenation of the compound having the structure:##STR76## using a palladium catalyst at temperatures in the range offrom about 130° up to about 170° C. and pressures in the range of fromabout 40 psig up to about 100 psig in accordance with the reaction:##STR77##

The compound having the structure: ##STR78## is produced as a byproductand this genus of compounds also has valuable organoleptic utilities.The compounds having the structure: ##STR79## may be used for theirorganoleptic properties "as is" or they may be further reacted with analdehyde defined according to the structure: ##STR80## in order to formthe compound having the structure: ##STR81## (in the presence ofhydrogen chloride gas) and the compounds having the structure: ##STR82##may then be hydrogenated in order to form compounds defined according tothe genus having the structure: ##STR83## wherein R₁ " represents C₁ -C₆alkyl and R₂ represents methyl or ethyl. This sequence of reactions isas follows: ##STR84##

The reaction: ##STR85## proceeds in the presence of hydrogen chloridegas at a temperature in the range of from about -10° C. up to about +10°C. and in the presence of a solvent inert to the reactants or productssuch as toluene or xylene. The mole ratio of aldehyde defined accordingto the structure: ##STR86## to ketone defined according to thestructure: ##STR87## may vary from about 0.5:1.5 up to about 1.5:0.5with a preferred mole ratio of about 1:1 being most expedient.

The reaction: ##STR88## proceeds using a palladium on carbon orpalladium on calcium carbonate catalyst, e.g., 10% palladium on carbonat a pressure in the range of 35 psig up to about 150 psig in thepresence of an inert solvent such as isopropyl alcohol. At the end ofthe reaction, the reaction mass is distilled preferably using afractional distillation column in order to yield the desired products.

The compounds of our invention defined according to the structure:##STR89## wherein R₁ represents C₁ -C₇ alkyl and R₂ represents methyl orethyl may also be prepared according to the process of Huffman andSawdaye, Cynth. Comm. 11(12) 979-81 (1981), that is, according to thereaction sequence: ##STR90## Thus, an alkyl acrylate having thestructure: ##STR91## may be reacted with a malonic acid ester having thestructure: ##STR92## in order to form the cyclic keto triester havingthe structure: ##STR93## according to the reaction: ##STR94## whereinR₅, R₆ and R₇ represent the same or different methyl or ethyl. Thereaction is carried out in the presence of base such as sodium hydrideor potassium hydride and in the presence of a solvent such as toluene,xylene or dimethylformanide or mixtures of same. The reaction is carriedout at reflux temperatures for a period of between about two and aboutten hours and at pressures of between one atmosphere and about fouratmospheres. At the end of the reaction the reaction product definedaccording to the structure: ##STR95## is distilled and further reactedwith a C₁ -C₇ alkyl halide defined according to the structure:

    R.sub.1 --X

wherein X is chloro, bromo or iodo and R₁ is C₁ -C₇ alkyl according tothe reaction: ##STR96## in order to form the compound having thestructure: ##STR97## this reaction is carried out in a strong base suchas potassium-t-butoxide in a compatible but inert solvent such ast-butanol. The reaction is also carried out at reflux conditions. Themole ratio of the compound having the structure: ##STR98## to thecompound having the structure:

    R.sub.1 --X

is about 1:1 with a slight excess of the compound having the structure:

    R.sub.1 --X

being preferred. At the end of the reaction, the resulting compoundhaving the structure: ##STR99## is decyclized and saponified using basefollowed by acid and the resulting product is decarboxylated to yieldthe tricarboxcylic acid having the structure: ##STR100## according tothe reaction: ##STR101## The saponification and decarboxylation arecarried out according to standard saponification and decarboxylationconditions. The resulting triester having the structure: ##STR102## isthen esterified with any desired alkanol such as methanol or ethanolhaving the structure:

    R.sub.8 --OH

according to the standard esterification reaction: ##STR103## therebyyielding the triester having the structure: ##STR104## This triester isthen cyclized according to the reaction: ##STR105## in the presence ofbase such as potassium-t-butoxide and solvent such as toluene, xylene,dimethylformamide or mixtures of same. This reaction takes place atreflux conditions and is operated in such a way as, during the reaction,the alkanol of reaction is distilled. At the end of the reaction, thereaction mass is decarboxylated according to the reaction: ##STR106##The decarboxylation reaction is carried out at temperatures of betweenabout 200° and about 300° C. at pressures of from about 1 up to about 5atmospheres. The reaction product having the structure: ##STR107## isthen distilled using fractional distillation in order to yieldorganoleptically desirable product. R₈ can be methyl or ethyl and R₁ isC₁ -C₇ alkyl.

The compound defined according to the structure: ##STR108## wherein R₁is C₁ -C₇ alkyl and R₂ is methyl or ethyl may also be produced by meansof first reacting the compound defined according to the structure:##STR109## with a lithium dialkyl amide according to the reaction:##STR110## whereby the lithium salt having the structure: ##STR111## isproduced (wherein R₃ and R₄ are the same or different and eachrepresents C₁ -C₄ alkyl). This reaction is carried out in the presenceof an inert solvent such as tetrahydrofuran at temperatures in the rangeof -80° up to -20° C. The resulting lithium salt having the structure:##STR112## is then reacted with an alkyl halide such as ethyl iodidedefined according to the structure:

    R.sub.1 --X

wherein R₁ is C₁ -C₇ and X is chloro, bromo or iodo according to thereaction: ##STR113## The second reaction: ##STR114## is carried out "insitu" without isolation of the lithium salt having the structure:##STR115## preferably and is carried out under the same range ofreaction conditions as the first reaction.

In each of the reactions the mole ratios of reactants are preferablyabout 1:1. Thus, the mole ratio of compound defined according to thestructure:

    R.sub.1 --X

to lithium salt having the structure: ##STR116## is about 1:1 and themole ratio of lithium dialkyl amide to the compound defined according tothe structure: ##STR117## is also about 1:1.

At the end of the reaction, as stated supra, the reaction product isextracted from the reaction mass or the reaction mass is washed, forexample, with saturated sodium chloride. The reaction product is thendistilled, preferably by means of vacuum distillation using afractionation column.

Examples of the products of our invention and their organolepticproperties as produced by means of one of the foregoing processes are asfollows:

                  TABLE I                                                         ______________________________________                                                        Food                                                          Structure of    Flavor      Perfumery                                         Compound        Properties  Properties                                        ______________________________________                                         ##STR118##     A nutty aroma and taste with a blueberry fla- vor at 20                       ppm.        A fruity and woody aroma with woody and                                       ionone-like nu- ances on dry-out.                  ##STR119##     A raspberry kernel aroma and taste at 1                                                   A strawberry- like, raspberry- like, and                                      green aroma with sweet raspberry-like and                                     licorice nuances on dry-out.                       ##STR120##     A tart, unrip- ened lime  aroma and taste  at 4                                           A fresh floral, jasmine-like and lemony aroma                                 ith jasmine-like and citrusy (lem- on)                                        nuances.                                           ##STR121##     A bitter lemon aroma and taste profile at 8                                               A jasmine-like aroma with cit- rusy                                           undertones.                                        ##STR122##     A dry lime citrusy aroma and taste pro- file at 3                                         An intense jas- mine, green aroma profile.         ##STR123##     A caramel-like, maple sugar- like, aroma and taste                            profile at  2 ppm.                                                                        A burnt maple aroma profile.                       ##STR124##     A maple/hazel- nut aroma and taste profile at 5                                           A maple/nutty aroma.                               ##STR125##     An intense co- coa aroma and taste profile with coffee                        nu- ances at 1 ppm.                                                                       A meaty, cocoa and coffee aroma profile.           ##STR126##     A fresh almond aroma and taste profile at 10                                              A valerian-like, green aroma with a toasted                                   almond undertone.                                 ______________________________________                                    

When one of the alkyl substituted and unsubstituted paracarboalkoxycyclohexanones of our invention is used as food flavor adjuvant, thenature of the coingredients included with one of the alkyl substitutedand unsubstituted para-carboalkoxy cyclohexanones in formulating theproduct composition will also serve to alter, modify, augment or enhancetheir organoleptic characteristics of the ultimate foodstuff treatedtherewith.

As used herein in regard to flavors, the term "alter", "modify" and"augment" in their various forms mean "supplying or imparting flavorcharacter or note to otherwise bland, relatively tasteless substances oraugmenting the existing flavor characteristic where the natural flavoris deficient in some regard or supplementing the existing flavorimpression to modify its quality, character or taste".

The term "enhance" is used herein to mean the intensification of aflavor or aroma characteristic or note without the modification of thequality thereof. Thus, "enhancement" of a flavor or aroma means that theenhancement agent does not add any additional flavor note.

As used herein, the term "foodstuff" includes both solid and liquidingestible materials which usually do, but need not, have nutritionalvalue. Thus, foodstuffs include soups, convenience foods, beverages,dairy products, candies, vegetables, cereals, soft drinks, snacks andthe like.

Substances suitable for use herein as co-ingredients or flavoringadjuvants are well known in the art for such use, being extensivelydescribed in the relevant literature. It is a requirement that any suchmaterial be "ingestibly" acceptable and thus non-toxic and otherwisenon-deleterious particularly from an organoleptic standpoint whereby theultimate flavor and/or aroma of the consumable material used is notcaused to have unacceptable aroma and taste nuances. Such materials mayin general be characterized as flavoring adjuvants or vehiclescomprising broadly stabilizes, thickeners, surface active agents,conditioners, other flavorants and flavor intensifiers.

Stabilizer compounds include preservatives, e.g., sodium chloride;antioxidants, e.g, calcium and sodium ascorbate, ascorbic acid,butylated hydroxy-anisole (mixture of 2- and 3-tertiary-butyl 4-hydroxyanisole), butylated hydroxy toluene(2,5-di-tertiary-butyl-4-methylphenol), propyl gallate and the like and sequestrants, e.g., citricacid.

Thickener compounds include carriers, binders, protective colloids,suspending agents, emulsifiers and the like, e.g., agar, carrageenan;cellulose and cellulose derivatives such as carboxymethyl cellulose andmethyl cellulose; natural and synthetic gums such as gum arabic, gumtragacanth; gelatin, proteinaceous materials; lipids; carbohydrates;starches, pectins and emulsifiers, e.g., mono- and diglycerides of fattyacids, skim milk powder, hexoses, pentoses, disacchardies, e.g., sucrosecorn syrup and the like.

Surface active agents include emulsifying agents, e.g., fatty acids suchas capric acid, caprylic acid, palmitic acid, myristic acid and thelike, mono- and diglycerides of fatty acids, lecithin, defoaming andflavor-dispersing agents such as sorbitan monostearate, potassiumstearate, hydrogenated tallow alcohol and the like.

Conditioners include compounds such as bleaching and maturing agents,e.g., benzoyl peroxide, calcium peroxide, hydrogen peroxide and thelike; starch modifiers such as peracetic acid, sodium chlorite, sodiumhypochlorite, propylene oxide, succinic anhydride and the like, buffersand neutralizing agents, e.g., sodium acetate, ammonium bicarbonate,ammonium phosphate, citric acid, lactic acid, vinegar and the like;colorants, e.g., carminic acid, cochineal, tumeric and curcuma and thelike; firming agents such as aluminum sodium sulfate, calcium chlorideand calcium gluconate; texturizers, anti-caking agents, e.g., aluminumcalcium sulfate and tribasic calcium phosphate; enzymes; yeast foods,e.g., calcium lactate and calcium sulfate; nutrient supplements, e.g,iron salts such as ferric phosphate, ferrous gluconate and the like,riboflavin, vitamins, zinc sources such as zinc chloride, zinc sulfateand the like.

Other flavorants and flavor intensifiers include organic acids, e.g.,acetic acid, formic acid, 2-hexenoic acid, benzoic acid, n-butyric acid,caproic acid, caprylic acid, cinnamic acid isobutyric acid, isovalericacid, alpha-methyl-butyric acid, propionic acid, valeric acid,2-methyl-2-pentenoic acid and 2-methyl-3-pentenoic acid; ketones andaldehydes, e.g., acetaldehyde, acetophenone, acetone, acetyl methylcarbinol, acrolein, n-butanal, crotonal, diacetyl, 2-methyl butanal,beta, beta-dimethylacrolein, methyl-n-amyl ketone, n-hexenal, 2-hexenal,isopentanal, hydrocinnamic aldehyde, cis-3-hexenal, 2-heptanal, nonylaldehyde, 4-(p-hydroxyphenyl)-2-butanone, alpha-ionone, beta-ionone,methyl-3-butanone, benzaldehyde, damascone, damascenone, acetophenone,2-heptanone, o-hydroxyacetophenone, 2-methyl-2-hepten-6-one, 2-octanone,2-undecanone, 3-phenyl-4-pentenal, 2-phenyl-2-hexenal,2-phenyl-2-pentenal, furfural, 5-methyl furfural, cinnamaldehyde,beta-cyclohomocitral, 2-pentanone, 2-pentenal and propanal; alcoholssuch as 1-butanol, benzyl alcohol, 1-borneol, trans-2-buten-1-ol,ethanol, geraniol, 1-hexanal, 2-heptanol, trans-2-hexenol-1,cis-3-hexen-1-ol, 3-methyl-3-buten-1-ol, 1-pentanol, 1-penten-3-ol,p-hydroxyphenyl- 2-ethanol, isoamyl alcohol, isofenchyl alcohol,phenyl-2-ethanol, alpha-terpineol, cis-ter-pineol hydrate, eugenol,linalool, 2-heptanol, acetaoin; esters, such as butyl acetate, ethylacetate, ethyl acetoacetate, ethyl benzoate, ethyl butyrate, ethylcaprate, ethyl caproate, ethyl caprylate, ethyl cinnamate, ethylcrotonate, ethyl formate, ethyl isobutyrate, ethyl isovalerate, ethyllaurate, ethyl myristate, ethyl alpha-methylbutyrate, ethyl propionate,ethyl salicylate, trans-2-hexenyl acetate, hexyl acetate, 2-hexenylbutyrate, hexyl butyrate, isoamyl acetate, isopropyl butyrate, methylacetate, methyl butyrate, methyl caproate, methyl isobutyrate,alpha-methylphenylglycidate, ethyl succinate, isobutyl cinnamate,cinnamyl formate, methyl cinnamate and terpenyl acetate; hydrocarbonssuch as dimethyl naphthalene, dodecane, methyl diphenyl, methylnaphthalene, myrcene, naphthalene, octadecane, tetradecane, tetramethylnaphthalene, tridecane, trimethyl naphthalene, undecane, caryophyllene,1-phellandrene, p-cymene, 1-alphapinene; pyrazines such as2,3-dimethylpyrazine, 2,5-dimethylpyrazine, 2,6-dimethylpyrazine,3-ethyl-2,5-dimethylpyrazine, 2-ethyl-3,5,6-trimethylpyrazine,3-isoamyl-2,5-dimethylpyrazine, 5-isoamyl-2,3-dimethylpyrazine,2-isoamyl-3,5,6-trimethylpyrazine, isopropyl dimethylpyrazine, methylethylpyrazine, tetramethylpyrazine, trimethylpyrazine; essential oils,such as jasmine absolute, cassia oil, cinnamon bark oil, rose absolute,orris absolute, lemon essential oil, Bulgarian rose, yara yara andvanilla; lactones such as δ-nonalactone; sulfides, e.g., methyl sulfideand other materials such as maltol, acetoin and acetals (e.g.,1,1-diethoxyethane, 1,1-dimethoxyethane and dimethoxymethane).

The specific flavoring adjuvant selected for use may be either solid orliquid depending upon the desired physical form of the ultimate product,i.e., foodstuff, whether simulated or natural, and should, in any event,(i) be organoleptically compatible with alkyl substituted andunsubstituted para-carboalkoxy cyclohexanones of our invention by notcovering or spoiling the organoleptic properties (aroma and/or taste)thereof; (ii) be non-reactive with the alkyl substituted andunsubstituted para-carboalkoxy cyclohexanones of our invention; and(iii) be capable of providing an environment in which the alkylsubstituted and unsubstituted para-carboalkoxy cyclohexanones of ourinvention can be dispersed or admixed to provide a homogeneous medium.In addition, selection of one or more flavoring adjuvants, as well asthe quantities thereof will depend upon the precise organolepticcharacter desired in the finished product. Thus, in the case offlavoring compositions, ingredient selection will vary in accordancewith the foodstuff, chewing gum, medicinal product or toothpaste towhich the flavor and/or aroma are to be imparted, modified, altered orenhanced. In contradistinction, in the preparation of solid products,e.g, simulated foodstuffs, ingredients capable of providing normallysolid compositions should be selected such as various cellulosederivatives.

As will be appreciated by those skilled in the art, the amount of alkylsubstituted and unsubstituted para-carboalkoxy cyclohexanones employedin a particular instance can vary over a relatively wide range,depending upon the desired organoleptic effects to be achieved. Thus,correspondingly, greater amounts would be necessary in those instanceswherein the ultimate food composition to be flavored is relatively blandto the taste, whereas relatively minor quantities may suffice forpurposes of enhancing the composition merely deficient in natural flavoror aroma. The primary requirement is that the amount selected to beeffective, i.e., sufficient to alter, modify or enhance the organolepticcharacteristics of the parent composition, whether foodstuff per se,chewing gum per se, medicinal product per se, toothpaste per se, orflavoring composition.

The use of insufficient quantities of alkyl substituted andunsubstituted para-carboalkoxy cyclohexanones will, of course,substantially vitiate any possibility of obtaining the desired resultswhile excess quantities prove needlessly costly and in extreme cases,may disrupt the flavor aroma balance, thus proving self-defeating.Accordingly, the terminology "effective amount" and "sufficient amount"is to be accorded a significance in the context of the present inventionconsistent with the obtention of desired flavoring effects.

Thus, and with respect to ultimate food compositions, chewing gumcompositions, medicinal product compositions and toothpastecompositions, it is found that quantities of alkyl substituted andunsubstituted para-carboalkoxy cyclohexanones ranging from a small buteffective amount, e.g., 0.5 ppm up to about 100 ppm based on totalcomposition are suitable. Concentrations in excess of the maximumquantity stated are not normally recommended, since they fail to provecommensurate enhancement of organoleptic properties. In those instances,wherein the alkyl substituted and unsubstituted para-carboalkoxycyclohexanones is added to the foodstuff as an integral component of aflavoring composition, it is, of course, essential that the totalquantity of flavoring composition employed be sufficient to yield aneffective concentration of the alkyl substituted and unsubstitutedpara-carboalkoxy cyclohexanones in the foodstuff product.

Food flavoring compositions prepared in accordance with the presentinvention preferably contain the alkyl substituted and unsubstitutedpara-carboalkoxy cyclohexanones in concentrations ranging from about0.1% up to about 15% by weight based on the total weight of the saidflavoring composition.

The composition described herein can be prepared according toconventional techniques well known as typified by cake batters and fruitdrinks and can be formulated by merely admixing the involved ingredientswithin the proportions stated in a suitable blender to obtain thedesired consistency, homogeneity of dispersion, etc. Alternatively,flavoring compositions in the form of particulate solids can beconveniently prepared by mixing the alkyl substituted and unsubstitutedpara-carboalkoxy cyclohexanones with, for example, gum arabic, gumtragacanth, carrageenan and the like, and thereafter spray-drying theresultant mixture whereby to obtain the particular solid product.Pre-prepared flavor mixes in powder form, e.g., a fruit-flavored powdermix are obtained by mixing the dried solid components, e.g., starch,sugar and the like and the alkyl substituted and unsubstitutedpara-carboalkoxy cyclohexanones in a dry blender until the requisitedegree of uniformity is achieved.

It is presently preferred to combine with the alkyl substituted andunsubstituted para-carboalkoxy cyclohexanones of our invention, thefollowing adjuvants:

p-Hydroxybenzyl acetone;

Geraniol;

Cassia Oil;

Acetaldehyde;

Maltol;

Ethyl methyl phenyl glycidate;

Benzyl acetate;

Dimethyl sulfide;

Eugenol;

Vanillin;

Caryophyllene;

Methyl cinnamate;

Guiacol;

Ethyl pelargonate;

Cinnamaldehyde;

Methyl Anthranilate;

5-Methyl furfural;

Isoamyl acetate;

Isobutyl acetate;

Cuminaldehyde;

Alpha ionone;

Cinnamyl formate;

Ethyl butyrate;

Methyl cinnamate;

Acetic acid;

Gamma-undecalactone;

Naphthyl ethyl ether;

Diacetyl;

Furfural;

Ethyl acetate;

Anethole;

2,3-Dimethyl pyrazine;

2-Ethyl-3-methyl pyrazine;

3-Phenyl-4-pentenal;

2-Phenyl-2-hexenal;

2-Phenyl-2-pentenal;

3-Phenyl-4-pentenal diethyl acetal;

β-Damascone

(1-crotonyl-2,2,6-trimethylcyclohex-1-ene);

β-Damascenone

(1-crotonyl-2,2,6-trimethylcyclohexa-1,3-diene);

Beta-cyclohomocitral

(2,2,6-trimethylcyclohex-1-ene carboxaldehyde);

Isoamyl butyrate;

Cis-3-hexenol-1;

2-Methyl-2-pentenoic acid;

Elemecine

(4-allyl-1,2,6-trimethoxybenzene);

Isoelemecine

(4-propenyl-1,2,6-trimethoxybenzene); and

2-(4-Hydroxy-4-methylpentyl)norbornadiene.

The alkyl substituted and unsubstituted para-carboalkoxy cyclohexanonesand one or more auxiliary perfume ingredients, including for example,alcohols, aldehydes, ketones other than the alkyl substituted andunsubstituted para-carboalkoxy cyclohexanones of our invention, terpinichydrocarbons, nitriles, esters other than the alkyl substituted andunsubstituted para-carboalkoxy cyclohexanones of our invention,lactones, natural essential oils and synthetic essential oils, may beadmixed so that the combined odors of the individual components producea pleasant and desired fragrance, particularly and preferably in jasmineand rose fragrances. Such perfume compositions usually contain (a) themain note or the "bouquet" or foundation stone of the composition; (b)modifiers which round off and accompany the main note; (c) fixativeswhich include odorous substances which lend a particular note to theperfume throughout all stages of evaporation and substances which retardevaporation; and (d) topnotes which are usually low boiling freshsmelling materials.

In perfume compositions, it is the individual components whichcontribute to their particular olfactory characteristics, however theover-all sensory effect of the perfume composition will be at least thesum total of the effects of each of the ingredients. Thus, at least oneof the alkyl substituted and unsubstituted para-carboalkoxycyclohexanones of our invention can be used to alter, modify or enhancethe aroma characteristics of a perfume composition, for example, byutilizing or moderating the olfactory reaction contributed by anotheringredient in the composition.

The amount of one or more of the alkyl substituted and unsubstitutedpara-carboalkoxy cyclohexanones of our invention which will be effectivein perfume compositions as well as in perfumed articles and colognesdepends on many factors, including the other ingredients, their amounts,and the effects which are desired. It has been found that perfumecompositions containing as little as 0.01% of at least one of the alkylsubstituted and unsubstituted para-carboalkoxy cyclohexanones of ourinvention or even less (e.g., 0.005%) can be used to impart, augment orenhance fruity, woody, strawberry, raspberry, green, fresh floral,jasmine-like, lemony, burnt maple, maple/nutty, meat/cocoa/coffee andvalerian-like aromas with woody, ionone-like, sweet raspberry-like,licorice-like, jasmine-like, citrusy, lemon and toasted almondundertones to soaps, cosmetics, solid or liquid anionic, cationic,nonionic or zwitterionic detergents, fabric softener compositions,fabric softener articles, hair preparations and perfumed polymers. Theamount employed can range up to 70% of the fragrance components and willdepend on considerations of cost, nature of the end product, the effectdesired on the finished product and the particular fragrance sought.

One or more of the alkyl substituted and unsubstituted para-carboalkoxycyclohexanones of our invention are useful [taken alone or together withother ingredients in perfume compositions] as (an) olfactorycomponent(s) in detergents and soaps, space odorants and deodorants,perfumes, colognes, toilet water, bath preparations, such as creams,deodorants, hand lotions and sun screens; powders such as talcs, dustingpowders, face powders and the like. When used as (an) olfactorycomponent(s) as little as 1% of the at least one of the alkylsubstituted and unsubstituted para-carboalkoxy cyclohexanones of ourinvention or even less will suffice to impart intense fruity, woody,strawberry-like, raspberry-like, green, fresh floral, jasmine-like,lemony, burnt maple, maple/nutty, meat, cocoa, coffee-like, andvalerian-like aromas with woody, ionone-like, sweet raspberry-like,licorice-like, jasmine-like, citrusy, lemony, and toasted almondundertones to rose formulations and jasmine formulations. Generally, nomore than 20% of at least one of the alkyl substituted and unsubstitutedpara-carboalkoxy cyclohexanones of our invention based on the ultimateend product is required in the perfume composition.

Accordingly, in perfume compositions and colognes from about 0.01% up toabout 70% of the perfume composition may be at least one of the alkylsubstituted and unsubstituted para-carboalkoxy cyclohexanones of ourinvention. In perfumed articles, the quantity of at least one of thealkyl substituted and unsubstituted para-carboalkoxy cyclohexanones ofour invention in the perfumed article may vary from about 0.005% up toabout 25% of the perfumed article in the case of perfumed polymers, forexample, and up to about 8% in the case of solid or liquid anionic,cationic, nonionic or zwitterionic detergents, for example.

In addition, the perfume composition or fragrance composition of ourinvention can contain a vehicle, or carrier for at least one of thealkyl substituted and unsubstituted para-carboalkoxy cyclohexanones ofour invention. The vehicle can be a liquid such as a non-toxic alcohol,such as ethyl alcohol or a non-toxic glycol, such as propylene glycol orthe like. The carrier can also be an absorbent solid, such as a gum(e.g., gum arabic xanthan gum, or guar gum or mixtures of same) orcomponents for encapsulating the composition (such as gelatin as bymeans of coacervation or such as a ureaformaldehyde prepolymer when sucha polymeric wall is formed around a liquid perfume composition center).

Furthermore, one or more of the alkyl substituted and unsubstitutedpara-carboalkoxy cyclohexanones of our invention are capable ofsupplying and/or potentiating certain flavor and aroma notes usuallylacking in many tobacco flavors heretofore provided.

As used herein in regard to tobacco flavors, the terms "alter" and"modify" in their various forms mean "supplying or imparting flavorcharacter or note to otherwise bland tobacco tobacco substitutes, ortobacco flavor formulations or augmenting the existing flavorcharacteristic where a natural flavor is deficient in some regard orsupplementing the existing flavor impression to modify its quality,character or taste".

As used herein, the term "enhance" is intended to mean theintensification (without change in kind of quality of aroma or taste) ofone or more taste and/or aroma nuances present in the organolepticimpression of tobacco or a tobacco substitute or a tobacco flavor.

Our invention thus provides an organoleptically improved smoking tobaccoproduct and additives therefor, as well as methods of making the samewhich overcome specific problems heretofore encountered in whichspecific desired floral, musty, hay-tea-like, sweet and fruity aroma andtaste nuances thereof, are created or enhanced and may be readilycontrolled and maintained at the desired uniform level regardless ofvariations in the tobacco components of the blend.

This invention further provides improved tobacoo additives and methodswhereby various floral, musty, hay-tea-like, sweet and fruity notes maybe imparted to smoking tobacco products and may be readily varied andcontrolled to produce the desired uniform flavor characteristics.

In carrying out this aspect of our invention, we add to smoking tobaccomaterials or a suitable substituted therefor (e.g., dried lettuceleaves) an aroma and flavor additive containing as an active ingredientat least one of the alkyl substituted and unsubstituted para-carboalkoxycyclohexanones of our invention.

In addition to at least one of the alkyl substituted and unsubstitutedpara-carboalkoxy cyclohexanones of our invention, other flavoring andaroma additives may be added to the smoking tobacco materials orsubstitute therefor either separately or in mixture with at least one ofthe alkyl substituted and unsubstituted para-carboalkoxy cyclohexanonesof our invention, other flavoring and aroma additives may be added tothe smoking tobacco materials or substitute therefor either separatelyor in mixture with at least one of the alkyl substituted andunsubstituted para-carboalkoxy cyclohexanones as follows:

(i) Synthetic Materials

Beta-ethyl-cinnamaldehyde;

Beta-cyclohomocitral;

Eugenol;

Dipentene;

Damascenone;

Damascone;

Maltol;

Ethyl Maltol;

Delta-undecalactone;

Delta-decalactone;

Benzaldehyde;

Amyl acetate;

Ethyl butyrate;

Ethyl valerate;

Ethyl acetate;

2-Hexenol-1;

2-Methyl-5-isopropyl-1,3-nonadiene-8-one;

2-6,Dimethyl-2,6-undecadiene-10-one;

2-Methyl-5-isopropyl acetophenone;

2-Hydroxy-2,5,5,8a-tetramethyl-1-(2-hydroxyethyl)decahydronaphthalene;

Dodecahydro-3a,6,6,9a-tetramethylnaphtho-[2,1,b]-furan;

4-Hydroxy hexanoic acid, gamma lactone; and

Polyisoprenoid hydrocarbons defined in Example V of U.S. Pat. No.3,589,372 issued on June 29, 1971.

(ii) Natural Oils

Celery seed Oil;

Coffee extract;

Bergamot Oil;

Cocoa extract;

Nutmeg Oil;

Origanum Oil.

An aroma and flavoring concentrate containing at least one of the alkylsubstituted and unsubstituted para-carboalkoxy cyclohexanones of ourinvention and, if desired, one or more of the above-indicated additionalflavoring additives may be added to the smoking tobacco material, to thefilter or to the leaf or paper wrapper. The smoking tobacco material maybe shredded, cured, cased and blended tobacco material or reconstitutedtobacco material or tobacco substitutes (e.g., lettuce leaves) ormixtures thereof. The proportions of flavoring additives may be variedin accordance with taste but insofar as enhancement or the imparting ofnatural and/or sweet notes, we have found that satisfactory results areobtained if the proportion by weight of the sum total of at least one ofthe alkyl substituted and unsubstituted para-carboalkoxy cyclohexanonesof our invention to smoking tobacco material is between 250 ppm and1,500 ppm (0.025%-0.15%) of the active ingredients to the smokingtobacco material. We have further found that satisfactory results areobtained if the proportion by weight of the sum total of at least one ofthe alkyl substituted and unsubstituted para-carboalkoxy cyclohexanonesof our invention and less than 50% used to flavoring material is between2,500 and 15,000 ppm (0.25%-1.5%).

Any convenient method for incorporating at least one of the alkylsubstituted and unsubstituted para-carboalkoxy cyclohexanones of ourinvention in the tobacco product may be employed. Thus, at least one ofthe alkyl substituted and unsubstituted para-carboalkoxy cyclohexanonesof our invention taken alone or along with other flavoring additives maybe dissolved in a suitable solvent such as ethanol, pentane, diethylether and/or other volatile organic solvents and the resulting solutionmay either be sprayed on the cured, cased and blended tobacco materialor the tobacco material may be dipped into such solution. Under certaincircumstances, a solution of at least one of the alkyl substituted andunsubstituted para-carboalkoxy cyclohexanones of our invention takenalone or taken further together with other flavoring additives as setforth above, may be applied by means of a suitable applicator such as abrush or roller on the paper or leaf wrapper for the smoking product, orit may be applied to the filter by either spraying, or dipping, orcoating.

Furthermore, it will be apparent that only a portion of the tobacco orsubstitute therefor need be treated and the thus treated tobacco may beblended with other tobaccos before the ultimate tobacco product isformed. In such cases, the tobacco treated may have at least one of thealkyl substituted and unsubstituted para-carboalkoxy cyclohexanones ofour invention in excess of the amounts or concentrations above-indicatedso that when blended with other tobaccos, the final product will havethe percentage within the indicated range.

In accordance with one specific example of our invention, an aged, curedand shredded domestic burley tobacco is sprayed with a 20% ethyl alcoholsolution of the compound having the structure: ##STR127## producedaccording to Example III or IV, infra, in an amount to provide a tobaccocomposition containing 800 ppm by weight of the compound having thestructure: ##STR128## on a dry basis. Thereafter, the alcohol is removedby evaporation and the tobacco is manufactured into cigarettes by theusual techniques. The cigarette when treated as indicated has a desiredand pleasing aroma (increased smoke body sensation in the mouth withenhanced tobacco-like notes and pleasant aromatic nuances) which isdetectable in the main and side streams when the cigarette is smoked.This aroma is described as having floral, musty, hay-tea-like, sweet andfruity notes.

While our invention is particularly useful in the manufacture of smokingtobacco, such as cigarette tobacco, cigar tobacco and pipe tobacco,other tobacco products formed from sheeted tobacco dust or fines mayalso be used. Likewise, at least one of the alkyl substituted andunsubstituted para-carboalkoxy cyclohexanones of our invention can beincorporated with materials such as filter tip materials, seam paste,packaging materials and the like which are used along with tobacco toform a product adapted for smoking. Furthermore, at least one of thealkyl substituted and unsubstituted para-carboalkoxy cyclohexanones ofour invention can be added to certain tobacco substitutes of natural orsynthetic origin (e.g., dried lettuce leaves) and, accordingly, by theterm "tobacco" as used throughout this specification is meant anycomposition intended for human consumption by smoking or otherwise,whether composed of tobacco plant parts or substitute materials or both.

The following Examples I-XII serve to illustrate the processes forpreparing the compounds of our invention and compounds useful for theirorganoleptic properties. Examples following Examples XII (Examples XIII,et seq) illustrate organoleptic utilities of the alkyl substituted andunsubstituted para-carboalkoxy cyclohexanones of our invention.

All parts and percentages given herein are by weight unless otherwisespecified.

EXAMPLE I PREPARATION OF 4-CARBOMETHOXY CYCLOHEXANONE

Reaction: ##STR129##

Into a 1-liter magnetically stirred autoclave is placed 488 grams ofmethyl-p-hydroxy benzoate having the structure: ##STR130## and 2.5 gramsof 5% palladium on carbon catalyst. The autoclave is sealed and hydrogenis pumped in while maintaining the contents of the autoclave at125°-130° C. and 50-70 psig pressure. After eighteen hours a GLC profileindicates that the reaction product contains 66% ketone having thestructure: ##STR131## 31% alcohol having the structure: ##STR132## and2% starting material having the structure: ##STR133## (conditions: 10%10'×0.25" carbowax column programmed at 225° C. isothermal).

In an additional example the reaction proceeds in a much lesser periodof timer increasing the amount of catalyst and running the reaction at ahigher temperature.

The reaction mass is then cooled, filtered and distilled through aneight plate vigreux column yielding the following fractions:

    ______________________________________                                                                           Weight                                               Vapor   Liquid    Vacuum of                                         Fraction  Temp.   Temp.     mm/Hg. Fraction                                   No.       (°C.)                                                                          (°C.)                                                                            Pressure                                                                             (gms)                                      ______________________________________                                        1         87      123       3.4/2.8                                                                              178.9                                      2         85      143       2.3    72.1                                       3         87      138       2.3    37.4                                       4         87      141       2.3    15.0                                       5         91      146       2.3    16.1                                       6         92      163       2.3    47.0                                       7         93      176       2.3    36.1                                       8         104     198       2.3    11.4                                       ______________________________________                                    

Fractions 13-16 are substantially all ketone having the structure:##STR134##

Fractions 25-27 are substantially all alcohol having the structure:##STR135##

FIG. 1 is the GLC profile of the crude reaction product prior todistillation. (Conditions: 10% carbowax 10'×0.25" column programmed at225° C., isothermal).

FIG. 2 is the infra-red spectrum for Fraction 4 of the foregoingdistillation containing the compound having the structure: ##STR136##

FIG. 3 is the NMR spectrum for Fraction of the foregoing distillationproduct. (Conditions: Field strength: 100 MHz; Solvent: CFCl₃).

The resulting compounds defined according to the structure: ##STR137##has a fruity and woody perfume aroma profile with woody and ionone-likenuances on dry-out. From a food flavor standpoint, it has a nutty aromaand taste with a blueberry flavor at 20 ppm.

EXAMPLE II PREPARATION OF 4-CARBOETHOXYCYCLOHEXANONE

Reaction: ##STR138##

Into a 1-liter magnetically stirred autoclave is placed 489 grams ofethyl-p-hydroxybenzoate having the structure: ##STR139## and 5%palladium on carbon catalyst (4 grams). The autoclave is sealed andhydrogenated at 125°-140° C. and 50 psig hydrogen pressure until theuptake of hydrogen is approximately 70% of theory. GLC analysisindicates that the reaction product at this point contains 71% ketonehaving the structure: ##STR140## 7.6% alcohol having the structure:##STR141## and 20% starting material having the structure: ##STR142##

The hydrogenation is carried during a period of ten hours (GLCconditions: 10'×0.125" 10% carbowax column programmed at 225° C.,isothermal).

At the end of the ten hour period, the autoclave is cooled and thereaction product is diluted with isopropyl alcohol and filtered. Theisopropyl alcohol is then removed by means of stripping and theremainder of the reaction mass is then distilled through a short pastcolumn to separate the resulting ketone and alcohol from the startingmaterial (boiling point: 2.4 mm/Hg at 90°-118° C.)

The ketone and alcohol cannot be separated by distillation. Accordingly,the alcohol having the structure: ##STR143## is converted to thecorresponding proprionate ester by means of stirring with 75 grams ofproprionic anhydride at 100° C. for a period of four hours, washing theresidue and distilling the resulting product through an eight platevigreux column yielding the following fractions:

    ______________________________________                                                                            Weight                                             Vapor    Liquid     Vacuum of                                        Fraction Temp.    Temp.      mm/Hg. Fraction                                  No.      (°C.)                                                                           (°C.)                                                                             Pressure                                                                             (gms)                                     ______________________________________                                        1-2      72-78    120/126    2.4    20.9                                      3-6      82-84    124        2.5    67.3                                      7-9      84       124-130    2.5    97.6                                      10-11     84-105  130-153    2.5    36.7                                      12       105      153        2.5    12.2                                      13-14    105-108  158-184    2.5    17.6                                      15-16    115      220        2.5    10.1                                      ______________________________________                                    

Fractions 3-12 of the foregoing distillation are substantially pureketone having the structure: ##STR144##

Fractions 13-16 of the foregoing distillation is substantially pureproprionate ester of the alcohol having the structure: ##STR145##

FIG. 4 is the NMR spectrum for Fraction 7 of the foregoing distillationcontaining the compound having the structure: ##STR146## (conditions:Field strength: 10 MHz; Solvent: CFCl₃).

FIG. 5 is the infra-red spectrum for Fraction 7 of the foregoingdistillation containing the compound having the structure: ##STR147##

The compound having the structure: ##STR148## from a perfumerystandpoint has a strawberry-like, raspberry-like and green aroma withsweet raspberry-like and licorice nuances on dry-out. From a flavorstandpoint it has an excellent raspberry kernel aroma and taste profileat 1 ppm.

EXAMPLE III PREPARATION OF 4-OXO-3-n-PENTYL-CYCLOHEXANE CARBOXYLIC ACID,METHYL ESTER

Reaction: ##STR149##

Into a 300 cc reaction vessel equipped with stirrer, thermometer, refluxcondensor and inlet hydrogen chloride gas tube is placed a mixture of 40ml toluene and 15.6 grams of keto ester having the structure: ##STR150##the reaction mass is cooled to 0° C. and is saturated with hydrogenchloride gas. 5 Grams of crystalline sodium sulfate is then added to thereaction mass with stirring. Over a period of one hour while maintainingthe reaction mass at 5°-10° C., a mixture of 40 ml toluene and 17.2grams of valeraldehyde is added. At the end of the one hour period, thereaction mass is permitted to warm up to room temperature. The reactionmass is then stirred for a period of three hours. The reaction mass isthen distilled on a one plate column yielding the compound having thestructure: ##STR151##

The resulting reaction product having the structure: ##STR152##

The resulting product has a GLC profile as illustrated in FIG. 6(conditions: 220° C. SE-30 isothermal). The peak indicated by referencenumeral "60" is the peak for the compound having the structure:##STR153##

The resulting compound having the structure: ##STR154## is then admixedwith 100 ml isopropyl alcohol and placed in a Parr shaker equipped withhydrogenation apparatus and containing 2 grams of a 10% palladium oncarbon catalyst. The reaction mass is then hydrogenated at a temperatureof 90°-100° C. and at a pressure of 8.5 atmospheres over a period offive hours. At the end of the five hour period, the reaction vessel isopened and the reaction mass if filtered.

FIG. 7 is the GLC profile of the resulting reaction product prior todistillation (conditions: SE-30, column programmed at 220° C.isothermal). The peak indicated by reference numeral "70" is the peakfor the compound having the structure: ##STR155##

The resulting product is distilled at a vapor temperature of 130° C. at3 mm/Hg pressure to yield the compound having a jasmine-like, citrusy,lemony aroma with fresh floral lemony undertones.

EXAMPLE IV PREPARATION OF 4-OXO-3-n-PENTYL-CYCLOHEXANE CARBOXYLIC ACID,METHYL ESTER

Reaction: ##STR156##

Into a 3-liter reaction vessel equipped with stirrer, thermometer,reflux condenser and hydrogen chloride inlet is placed a mixture of 400ml toluene and 290 grams of the ketoester having the structure:##STR157## The resulting mixture is cooled to 0° C. and is saturatedwith hydrogen chloride gas while maintaining the temperature of thereaction mass at 0° C. 57 Grams of sodium sulfate is then added to thereaction mass while permitting the temperature to remain at 5°-10° C.Over a period of two hours, a mixture of 400 ml toluene and 318.2 gramsof valeraldehyde is added to the reaction mass. At the end of the twohour period, the reaction mass is permitted to rise to room temperature.The reaction mass is maintained at 30° C. for a period of two hours. Atthe end of the reaction, the reaction mass is quenched with water andneutralized with sodium carbonate and then evaporated on a one platedistillation column.

The resulting product has the structure: ##STR158##

FIG. 8 is the GLC profile for the reaction product having the structure:##STR159## The peak indicated by reference numeral "80" is the peak forthe compound having the structure: ##STR160##

The reaction mass is then placed in a par shaker into which has beenpreviously placed 2 grams of 10% palladium on carbon catalyst and1.8-liters of anhydrous isopropanol. The parr shaker is sealed andhydrogenated to a pressure of 8.2 atmospheres at 180° C. for a period ofsix hours. At the end of the six hour period, the parr shaker is openedand the reaction mass is filtered. The resulting filtrate is distilledyielding the following fractions:

    ______________________________________                                                                           Weight                                               Vapor   Liquid    Vacuum of                                         Fraction  Temp.   Temp.     mm/Hg. Fraction                                   No.       (°C.)                                                                          (°C.)                                                                            Pressure                                                                             (gms)                                      ______________________________________                                        1         23/25   23/110    50/4   32.1                                       2          90     140       4.0    10.1                                       3         100     158       4.0    34.1                                       4         110     162       4.0    32.0                                       5         128     175       4.0     6.2                                       6         130     180       4.0    10.1                                       7         130     190       3.0     9.6                                       8         130     180       3.0     9.8                                       9         130     180       3.0    13.1                                       10        130     180       3.0    15.1                                       11        130     185       3.0    15.2                                       12        126     195       3.0    13.0                                       13        120     200       3.0     7.6                                       14        117     215       3.0     2.6                                       ______________________________________                                    

FIG. 8 is the GLC profile for the reaction product prior tohydrogenation containing the compound having the structure: ##STR161##

FIG. 9 is the GLC profile for the reaction product subsequent tohydrogenation containing the compound having the structure: ##STR162##The peak indicated by reference numeral "90" is the peak for thecompound having the structure: ##STR163##

FIG. 10 is the NMR spectrum for the compound having the structure:##STR164## (conditions: Field strength: 100 MHz; Solvent: CFCl₃).

FIG. 11 is the infra-red spectrum for the compound having the structure:##STR165##

The resulting product has a jasmine, citrus, lemony aroma with freshfloral jasmine, lemony undertones.

EXAMPLE V PREPARATION OF ETHYL ESTER OF 4-OXO-3-n-PENTYLCYCLOHEXANECARBOXYLIC ACID

Reaction: ##STR166##

Into a 5-liter reaction vessel equipped with heating mantle, stirrerthermometer, reflux condenser and hydrogen chloride gas inlet tube isplaced a mixture of 1-liter of toluene and 531 grams of the compoundhaving the structure: ##STR167## The resulting mixture is cooled to 0°C. and the mixture is then saturated with hydrogen chloride gas whilemaintaining the temperature at 0° C. 114 Grams of anhydrous sodiumsulfate is then added to the reaction mass. Over a period of 1.25 hours,a mixture of 533.2 grams of valeraldehyde and 1-liter of toluene isadded to the reaction mass while maintaining the reaction mass of 5°-10°C. At the end of the 1.25 hour addition period, the reaction mass isstirred at a temperature of 10° C. for a period of three hours. At theend of the three hour period, the reaction mass is washed with water andneutralized with sodium bicarbonate. The solvent is then evaporated on arotovap evaporater yielding the product having the structure: ##STR168##

FIG. 12 is the GLC profile for the compound having the structure:##STR169## produced as a result of this portion of the example. The peakindicated by reference numeral "121" is the peak for the compound havingthe structure: ##STR170##

The resulting reaction product is then added to an autoclave containing5 grams of 10% palladium on carbon and 1-liter of isopropyl alcohol. Theautoclave is sealed and hydrogen is added to a pressure of 3 atmospheresat a temperature of 140° C. for a period of nine hours. At the end ofthe nine hour period, the reaction vessel is opened and the reactionmass is filtered.

FIG. 13 is the GLC profile for the reaction product containing thecompound having the structure: ##STR171## The peak indicated byreference numeral "130" is the peak for the compound having thestructure: ##STR172## The reaction mass is then fractionally distilledat 4 mm/Hg. pressure and 135° C. to yield the compound having thestructure: ##STR173##

FIG. 14 is the NMR spectrum for the compound having the structure:##STR174## (conditions: Field strength: 100 MHz; Solvent: CFCl₃).

FIG. 15 is the infra-red spectrum for the compound having the structure:##STR175##

EXAMPLE VI PREPARATION OF METHYL ESTER OF 3-n-HEXYL-4-OXO-CYCLOHEXANECARBOXYLIC ACID

Reactions: ##STR176##

Into a 300 ml reaction flask equipped with stirrer, cooling bath, refluxcondenser, stirrer thermometer and hydrogen chloride gas inlet tube isplaced 50 ml toluene and 15.8 grams of ketoester having the structure:##STR177## The resulting mixture is cooled to 0° C. and whilemaintaining the mixture at 0° C. the mixture is saturated with hydrogenchloride gas. 5 Grams of anhydrous sodium sulfate is then added to thereaction mass. Over a period of two hours while maintaining the reactionmass at 5°-10° C. a mixture of 18 grams of n-hexanal and 50 ml tolueneis added to the reaction mass. The reaction mass is then stirred at 5°to 10° C. for a period of three hours. At the end of the three hourperiod, the reaction mass is washed with water and neutralized withsodium carbonate. The reaction mass is then stripped of solvent on a oneplate distillation column. The resulting product has the structure:##STR178##

The resulting product is then placed into an autoclave which alreadycontains 100 ml isopropyl alcohol and 0.5 grams of 10% palladium oncarbon catalyst. The autoclave is sealed and hydrogenated at atemperature of 140° C., a pressure of 4.5 atmospheres for a period oftime of seven hours. At the end of the seven hour period, the autoclaveis opened and the reaction mass is filtered and distilled. The reactionproduct has the structure: ##STR179##

FIG. 16 is the NMR spectrum for the compound having the structure:##STR180## (conditions: Field strength: 100 MHz; Solvent: CFCl₃).

FIG. 17 is the infra-red spectrum for the compound having the structure:##STR181##

The compound having the structure: ##STR182## has a valerian oil aromawith long lasting jasmine and green undertones.

EXAMPLE VII PREPARATION OF METHYL ESTER OF 4-OXO-3-n-PROPYL CYCLOHEXANECARBOXYLIC ACID

Reactions: ##STR183##

Into a 300 cc reaction flask equipped with stirrer thermometer, refluxcondenser cooling bath and hydrogen chloride inlet tube is placed amixture of 48 ml toluene and 15.8 grams of ketoester having thestructure: ##STR184## The resulting mixture is cooled to 0° C. andsaturated with hydrogen chloride gas while maintaining the temperatureat 0° C. The resulting mixture is then admixed with 5 grams of anhydroussodium sulfate. Over a period of one hour, a mixture of 50 ml tolueneand 11 grams of propionaldehyde is added to the reaction mass whilemaintaining the temperature at 5°-10° C. At the end of the one hourperiod, the reaction mass is then permitted to rise in temperature to30° C. The reaction mass is maintained at 30° C. for a period of 2.5hours. At the end of the 2.5 hour period, the reaction mass contains thecompound having the structure: ##STR185##

FIG. 18 is the GLC profile for the reaction mass at this pointcontaining the compound having the structure: ##STR186## The peakindicated by reference numeral "180" is the peak for the compound havingthe structure: ##STR187## (conditions: 10% SE-30 column programmed at180° C. isothermal).

The resulting product is then placed in an autoclave which contains 100ml isopropyl alcohol and 2 grams of 10% palladium on carbon catalyst.The autoclave is sealed and pressurized to 4 atmospheres pressure at140° C. for a period of seven hours with hydrogen. At the end of thehydrogenation period, the autoclave is cooled and opened and thecontents filtered. The resulting product has the structure: ##STR188##The resulting product has the GLC profile as set forth in FIG. 19 andcontains the compound having the structure: ##STR189## The peakindicated by reference numeral "190" is the peak for the compound havingthe structure: ##STR190## (conditions: 10% SE-30 column programmed at220° C. isothermal).

FIG. 20 is the NMR spectrum for the compound having the structure:##STR191## (conditions: Field strength: 100 MHz; Solvent: CFCl₃).

FIG. 21 is the infra-red spectrum for the compound having the structure:##STR192##

The resulting compound has a burnt maple aroma with pineapple-likeundertones.

EXAMPLE VIII PREPARATION OF METHYL ESTER OF 3-ISOBUTYL-4-OXOCYCLOHEXANECARBOXYLIC ACID

Reactions: ##STR193##

Into a 300 cc reaction vessel equipped with stirrer, thermometer, refluxcondenser, cooling coils and hydrogen chloride inlet tube is placed amixture of 50 ml toluene and 15.8 grams of the ketoester having thestructure: ##STR194## The reaction mass is cooled to 0° C. and whilemaintaining the reaction mass at 0° C., the reaction mass is saturatedwith anhydrous hydrogen chloride gas. 5 Grams of sodium sulfate is thenadded to the reaction mass. To the reaction mass over a period of onehour is added a mixture of 50 ml toluene and 13.0 grams ofisobutyraldehyde. The reaction mass is then permitted to rise intemperature from +10° C. up to +30° C. The reaction mass is then stirredat 30° C. for a period of 2.5 hours. At the end of the reaction, thereaction mass is neutralized with sodium carbonate and the solvent isevaporated on a roto vap evaporator. The resulting product has thestructure: ##STR195##

FIG. 22 is the GLC profile of the reaction product containing thecompound having the structure: ##STR196## The peak indicated byreference numeral "220" is the peak for the compound having thestructure: ##STR197## (conditions: 10% SE-30 column programmed at 180°C. isothermal).

The reaction product is then charged to an autoclave containing 100 mlisopropyl alcohol and 2 grams 10% palladium on carbon catalyst. Theautoclave is sealed and hydrogenated at a pressure of 4.5 atmospheresand a temperature of 143° C. for a period of six hours. At the end ofthe six hour period, the autoclave is cooled and opened and the contentsare filtered and distilled. The resulting reaction product contains thecompound having the structure: ##STR198##

FIG. 23 is the GLC profile for the reaction product containing thecompound having the structure: ##STR199## The peak indicated by thereference numeral "230" is the peak for the compound having thestructure: ##STR200## (conditions: 10% SE-30 column programmed at 220°C. isothermal).

FIG. 24 is the NMR spectrum for the compound having the structure:##STR201## (conditions: Field strength: 100 MHz; Solvent: CFCl₃).

FIG. 25 is the infra-red spectrum for the compound having the structure:##STR202## The resulting product has a maple, nutty aroma.

EXAMPLE IX PREPARATION OF METHYL ESTER OF 3-n-BUTYL-4-OXOCYCLOHEXANECARBOXYLIC ACID

Reactions: ##STR203##

Into a 300 cc reaction vessel equipped with stirrer thermometer, refluxcondenser and cooling coils is placed a mixture of 15.2 grams of theketoester having the structure: ##STR204## and 50 ml toluene. Theresulting mixture is cooled to 0° C. and is then saturated withanhydrous hydrogen chloride gas while maintaining the temperature at 0°C. At the end of the addition of the hydrogen chloride gas, 5 grams ofanhydrous sodium sulfate is added to the reaction mass. Whilemaintaining the reaction temperature at 5°-10° C. over a period of 0.5hours, a mixture of 50 ml toluene and 18.0 grams of n-butanal is addedwith stirring. The reaction mass is then permitted to rise intemperature to 30° C. over a period of 0.5 hours. The reaction mass isthen maintained with stirring at 30° C. for a period of 3.0 hours. Atthe end of the 3.0 hour period, the reaction mass is neutralized withsodium carbonate and the solvent is stripped from the reaction massusing a rotovap. The resulting product has the structure: ##STR205##

FIG. 26 is the GLC profile for the reaction mass containing the compoundhaving the structure: ##STR206## The peak indicated by reference numeral"260" is the peak for the compound having the structure: ##STR207##(conditions: 10% SE-30 column programmed at 180° C. isothermal).

The resulting product is then charged to an autoclave containing 100 mlisopropyl alcohol and 2 grams 10% cooked palladium on carbon catalyst.The autoclave is sealed and the reaction mass is pressurized to 5atmospheres pressure at 150° C. with hydrogen and maintained at thatpressure and temperature for a period of 5.5 hours. At the end of the5.5 hour period, the reaction mass is then cooled and the autoclave isopened and filtered. The resulting filtrate is distilled yielding theproduct having the structure: ##STR208## The peak indicated by referencenumeral "270" is the peak for the compound having the structure:##STR209##

FIG. 28 is the NMR spectrum for the compound having the structure:##STR210## (conditions: Field strength: 100 MHz; Solvent: CFCl₃).

FIG. 29 is the infra-red spectrum for the compound having the structure:##STR211##

The resulting product having the structure: ##STR212## has a meaty,cocoa and coffee aroma profile.

EXAMPLE X PREPARATION OF METHYL ESTER OF 3-ISOPENTYL-4-OXO-CYCLOHEXANECARBOXYLIC ACID

Reactions: ##STR213##

Into a 300 ml reaction flask equipped with stirrer, thermometer, coolingcoil, and hydrogen chloride inlet tube is placed a mixture 50 ml tolueneand 15.8 grams of ketoester having the structure: ##STR214## Theresulting mixture is cooled to -10° C. While maintaining the reactionmass at -10° C. the reaction mass is saturated with anhydrous hydrogenchloride gas. The reaction mass is maintained at -10° up to -5° C. and 5grams of anhydrous sodium sulfate is added. To the reaction mass, over aperiod of one hour, while maintaining the reaction mass at -10° up to-5° C., a mixture of 50 ml toluene and 18 grams of isovaleraldehyde isadded to the reaction mass. At the end of the feeding of the mixture ofisovaleraldehyde and toluene, the reaction mass temperature is allowedto rise to 30° C. The reaction mass is maintained at 30° C. withstirring for a period of 2.7 hours. At the end of the 2.7 hour period,the reaction mass is washed and neutralized with sodium carbonate andthe solvent is evaporated on a rotovap evaporator. The resultingreaction mass contains the compound having the structure: ##STR215##

The resulting reaction mass is then charged to an autoclave containing100 ml anhydrous isopropyl alcohol and 2 grams of 10% palladium oncarbon catalyst. The autoclave is sealed and pressurized with hydrogento a pressure of 5 atmospheres while maintaining the temperature at 170°C. for a period of six hours. At the end of the six hour period theautoclave is cooled and opened. The contents are filtered and distilledyielding the compound having the structure: ##STR216##

FIG. 30 is the NMR spectrum for the compound having the structure:##STR217## (conditions: Field strength: 100 MHz; Solvent: CFCl₃).

FIG. 31 is the infra-red spectrum for the compound having the structure:##STR218##

The resulting product has a valerian oil green aroma with pleasantalmond undertones.

EXAMPLE XI(A) PREPARATION OF TRIMETHYL ESTER OF 1-OXO-2,4,4-CYCLOHEXANETRICARBOXYLIC ACID

Reaction: ##STR219##

Into a 5-liter reaction vessel is placed 2,400 ml toluene and 184.8grams of sodium hydride. The resulting mixture is heated to 40° C. andover a period of 1.25 hours, dimethyl malonate is added (528 grams).Over a period of ten minutes, 800 ml dimethylformamide is added to thereaction mass. Over a period one hour, 705 grams of methyl acrylate isadded to the reaction mass. The reaction mass is then heated to refluxand refluxed for a period of four hours. At the end of the four hourperiod, the reaction mass is cooled down and quenched into 5-liters ofwater. The reaction mass is then distilled on a one plate short pathcolumn yielding 698.8 grams of product. The fractions yielded as aresult of this distillation are as follows:

    ______________________________________                                                                       Vacuum                                                   Vapor        Liquid  mm/Hg.                                         Fraction  Temp.        Temp.   Pressure                                       No.       (°C.) (°C.)                                                                          (gms)                                          ______________________________________                                        1         /46          /55     1.00                                           2          47           55     1.00                                           3         170          180     3.00                                           4         175          220     3.00                                           ______________________________________                                    

FIG. 32 is the NMR spectrum for the compound having the structure:##STR220## (Conditions: Field strength: 100 MHz; Solvent: CFCl₃).

FIG. 33 is the infra-red spectrum for the compound having the structure:##STR221##

EXAMPLE XI(B) PREPARATION OF TRIMETHYL ESTER OF1,3,5-n-DECANETRICARBOXYLIC ACID

Reactions: ##STR222## (wherein X represents bromo); and ##STR223##

2,4,4-Tricarbomethoxy cyclohexanone (271 grams) produced according toExample XI(A) is added to a solution of 123 grams ofpotassium-t-butoxide in t-butanol.

The resulting solution is heated to reflux whereupon 1-bromo pentane isadded over a period of one hour. The reaction mass is then stirred atreflux for a period of four hours.

400 Grams of 25% sodium hydroxide solution is then added while refluxingthe reaction mass. The resulting reaction mass is stirred at reflux fora period of two hours. The reaction mass is then cooled whereupon 500 mlof water is added. Concentrated hydrochloride acid (800 ml) is thenadded over a one hour period while maintaining the reaction mass at25°-40° C. accompanied by vigorous gas evolution. 200 Ml toluene is thenadded to the reaction mass and the organic solution is separated fromthe inorganic solution. The solvents are removed from the organicsolution on a rotary evaporator to afford 310 grams of viscous oil. Thisoil is dissolved in 400 ml methanol and treated with a stream ofanhydrous hydrogen chloride while refluxing at 82° C.

The reaction mass is then heated for six hours. Methanol is distilledaway from the crude reaction mass until a pot temperature of 100° C. isreached. The crude reaction mass is then cooled, triturated at 200 ml oftoluene and washed twice with water. Distillation affords 128 grams ofmethyl-4,6-dicarbomethoxyundecylenate (boiling point 185° C. at 1 mm/Hg.pressure) having the following structure: ##STR224##

FIG. 34 is the GLC profile of the reaction product containing thecompound having the structure: ##STR225## The peak indicated byreference numberal "340" is the peak for the compound having thestructure: ##STR226##

FIG. 35 is the NMR spectrum for the compound having the structure:##STR227## (conditions: Field strength: 100 MHz; Solvent: CFCl₃).

FIG. 36 is the infra-red spectrum for the compound having the structure:##STR228##

EXAMPLE XI(C) PREPARATION OF METHYL ESTER OF 4-OXO-3-n-PENTYLCYCLOHEXANECARBOXYLIC ACID

Reactions: ##STR229##

Methyl-4,6-dicarbomethoxyundecylenate (128 grams) having the structure:##STR230## prepared according to Example XI(B) is added to a solution of62 grams of potassium t-butoxide in 200 ml toluene and 300 mldimethylformamide.

The resulting slurry is heated to 140° C. while distilling off themethanol. The reaction mass is then aged at 148° C. for a period of twohours. The reaction mass is then cooled to 60° C. and poured into1-liter of water containing 80 ml of acetic acid. The organic layer isseparated from the inorganic layer. The resulting inorganic (aqueous)layer is extracted with 100 ml toluene. The combined toluene extract andorganic layer is then heated to 220° C. while distilling away solvent.At 220° C., 18 ml of water are added dropwise over a period of one hour.Methanol, water and carbon dioxide are evolved. The organic mass is thendistilled at 3 mm/Hg. pressure to afford 62 grams of2-n-pentyl-4-carbomethoxy cyclohexanone having the structure: ##STR231##

EXAMPLE XII PREPARATION OF METHYL ESTER OF 4-OXO-3-n-PENTYLCYCLOHEXANECARBOXYLIC ACID

Reactions: ##STR232##

To a stirred solution of 500 ml of lithium diisopropylamine intetrahydrofuran are added dropwise 156 grams of 4-carbomethoxycyclohexanone at -28° C. having the structure: ##STR233## The resultingsolution is stirred for 0.5 hours at -28° C. whereupon 1-bromopentane isadded with stirring and cooling. Just prior to the addition of the1-bromopentane the resulting product has the structure: ##STR234##

The resulting reaction mass is allowed to come to room temperature andis quenched into 3-liters of water. The resulting mixture is extractedthree times with diethyl ether (500 ml portions). The combined etherextracts are extracted with 500 ml of 10% sodium chloride solution. Theresulting organic mass is distilled to yield 100 grams of product havingthe structure: ##STR235## distilling at 130° C. at 3.1 mm/Hg. pressure.

EXAMPLE XIII

The alkyl substituted and unsubstituted para-carboalkoxy cyclohexanonesof our invention produced according to Examples I-XII inclusive havevery long lasting fruity, woody, strawberry, raspberry-like, green,fresh floral, jasmine-like, lemony, burnt maple, maple/nutty,cocoa-like, coffee-like and valerian oil-like aromas with woodyionone-like, sweet raspberry-like, licorice, jasmine-like and citrusyundertones which may be utilized to a great extent in inexpensivefunctional products. The following pine fragrance demonstrates the useof these materials in perfume compositions.

    __________________________________________________________________________                  PARTS BY WEIGHT                                                 INGREDIENTS   XIIIa                                                                             XIIIb                                                                             XIIIc                                                                             XIIId                                                                             XIIIe                                                                             XIIIf                                                                             XIIIg                                                                             XIIIh                                                                             XIIIi                                                                             XIIIj                                                                             XIIIk                   __________________________________________________________________________    Isobornyl acetate                                                                           100 100 100 100 100 100 100 100 100 100 100                     Camphor       10  10  10  10  10  10  10  10  10  10  10                      Terpineol     25  25  25  25  25  25  25  25  25  25  25                      Fir Balsam Absolute                                                                         20  20  20  20  20  20  20  20  20  20  20                      (50% in Diethyl Phthalate)                                                    Coumarin      4   4   4   4   4   4   4   4   4   4   4                       Linalool      30  30  30  30  30  30  30  30  30  30  30                      Anethol       2   2   2   2   2   2   2   2   2   2   2                       Fenchyl Alcohol                                                                             10  10  10  10  10  10  10  10  10  10  10                      Lemon Terpenes Washed                                                                       50  50  50  50  50  50  50  50  50  50  50                      Borneol       5   5   5   5   5   5   5   5   5   5   5                       Galbanum Oil  5   5   5   5   5   5   5   5   5   5   5                       Turpentine Russian                                                                          150 150 150 150 150 150 150 150 150 150 150                     Pinus Pumilionus                                                                            50  50  50  50  50  50  50  50  50  50  50                      Eucalyptol    50  50  50  50  50  50  50  50  50  50  50                      2,2,6-trimethyl-1-cyclo                                                                     5   5   5   5   5   5   5   5   5   5   5                       hexene-1-carboxaldehyde                                                       Maltol 1% in Diethyl                                                                        5   5   5   5   5   5   5   5   5   5   5                       Phthalate -Product produced according                                                       12  0   0   0   0   0   0   0   0   0   0                       to Example I having the                                                       structure:                                                                     ##STR236##                                                                   Product produced according                                                                  0   12  0   0   0   0   0   0   0   0   0                       to Example II                                                                 having the structure:                                                          ##STR237##                                                                   Product produced according                                                                  0   0   12  0   0   0   0   0   0   0   0                       to one of Examples III, IV,                                                   XI(C) or XII having the                                                       structure:                                                                     ##STR238##                                                                   Compound having the                                                                         0   0   0   12  0   0   0   0   0   0   0                       structure:                                                                     ##STR239##                                                                   produced according                                                            to Example V.                                                                 Compound having the                                                                         0   0   0   0   12  0   0   0   0   0   0                       structure:                                                                     ##STR240##                                                                   produced according to                                                         Example VI.                                                                   Compound having                                                                             0   0   0   0   0   12  0   0   0   0   0                       the structure:                                                                 ##STR241##                                                                   produced according                                                            to Example VII                                                                Compound having                                                                             0   0   0   0   0   0   12  0   0   0   0                       the structure:                                                                 ##STR242##                                                                   produced according                                                            to Example VIII.                                                              Compound having                                                                             0   0   0   0   0   0   0   12  0   0   0                       the structure:                                                                 ##STR243##                                                                   produced according to                                                         Example IX.                                                                   Compound having 0                                                                           0   0   0   0   0   0   0   12  0   0                           the structure:                                                                 ##STR244##                                                                   produced according to                                                         Example X.                                                                    50:50 Mixture of compounds                                                                  0   0   0   0   0   0   0   0   0   12  0                       having the structures:                                                         ##STR245##                                                                   and                                                                            ##STR246##                                                                   50:50 Mixture of compounds                                                                  0   0   0   0   0   0   0   0   0   0   12                      having the structures:                                                         ##STR247##                                                                   and                                                                            ##STR248##                                                                   __________________________________________________________________________

The following pine aromas are each modified by the various alkylsubstituted and unsubstituted para-carboalkoxy cyclohexanones ormixtures of same added to the basic pine aroma. Thus, the followingexamples can be described as having the following aromas:

    ______________________________________                                        Example No.                                                                             Description                                                         ______________________________________                                        XIIIa     Piney with fruity, woody and ionone-like                                      nuances with a strong woody ionone-like                                       undertone.                                                          XIIIb     Piney with strawberry-like, raspberry-like,                                   and green topnotes and sweet raspberry-like                                   and licorice undertones.                                            XIIIc     Piney with fresh floral, jasmine-like                                         and lemony topnotes and jasmine-like                                          and citrusy (lemon) undertones.                                     XIIId     Piney with jasmine topnotes and citrusy                                       undertones.                                                         XIIIe     Piney with jasmine and green topnotes.                              XIIIf     Piney with burnt maple topnotes.                                    XIIIg     Piney with maple/nutty topnotes.                                    XIIIh     Piney with cocoa-like and coffee-like                                         topnotes.                                                           XIIIi     Piney with valerian-like and green                                            topnotes and toasted almond undertones.                             XIIIj     Piney with jasmine-like topnotes.                                   XIIIk     Piney with valerian-like and green                                            topnotes.                                                           ______________________________________                                    

EXAMPLE XIV A COSMETIC POWDER PREPARATION

A cosmetic powder is prepared by mixing in a ball mill 100 grams oftalcum powder with 0.25 grams of one of the substances set forth inTable I below containing at least one of the alkyl substituted andunsubstituted para-carboalkoxy cyclohexanones of our invention. Each ofthe cosmetic powders has an excellent aroma as described in Table Ibelow.

                  TABLE I                                                         ______________________________________                                        Perfumery Substance                                                                            Aroma Nuance                                                 ______________________________________                                         ##STR249##      A fruity and woody aroma with woody and ionone-like                           nuances.                                                     produced according to                                                         Example I.                                                                     ##STR250##      A strawberry, raspberry and green aroma with sweet                            raspberry-like and licorice nuances on dry-out.              produced according to                                                         Example II.                                                                    ##STR251##      A fresh floral, jasmine-like and lemony aroma with                            jasmine- like, citrusy and lemony nuances.                   produced according to                                                         one of Examples III,                                                          IV, XI(C) or XII.                                                             Compound having the                                                                            A jasmine-like aroma with                                    structure:       citrusy undertones.                                           ##STR252##                                                                   produced according to                                                         Example V.                                                                    Compound having the                                                                            A jasmine, green aroma.                                      structure:                                                                     ##STR253##                                                                   produced according to                                                         Example VI.                                                                   Compound having the                                                                            A burnt maple aroma.                                         structure:                                                                     ##STR254##                                                                   produced according to                                                         Example VII.                                                                  Compound having the                                                                            A maple/nutty aroma.                                         structure:                                                                     ##STR255##                                                                   produced according to                                                         Example VIII.                                                                  ##STR256##      A cocoa and coffee aroma profile with pyrazine-like                           undertones.                                                  produced according to                                                         Example IX.                                                                    ##STR257##      A valerian oil-like, green  aroma with toasted almond                         undertones.                                                  produced according to                                                         Example X.                                                                    Perfume composition                                                                            Piney with fruity, woody and                                 of Example XIIIa.                                                                              ionone-like nuances with a                                                    strong woody ionone-like                                                      undertone.                                                   Perfume composition                                                                            Piney with strawberry-like,                                  of Example XIIIb.                                                                              raspberry-like, and green                                                     topnotes and sweet raspberry-                                                 like and licorice undertones.                                Perfume composition                                                                            Piney with fresh floral,                                     of Example XIIIc.                                                                              jasmine-like and lemony                                                       topnotes and jasmine-like                                                     and citrusy (lemon) undertones.                              Perfume composition                                                                            Piney with jasmine topnotes                                  of Example XIIId.                                                                              and citrusy undertones.                                      Perfume composition                                                                            Piney with jasmine and green                                 of Example XIIIe.                                                                              topnotes.                                                    Perfume composition                                                                            Piney with burnt maple                                       of Example XIIIf.                                                                              topnotes.                                                    Perfume composition                                                                            Piney with maple/nutty                                       of Example XIIIg.                                                                              topnotes.                                                    Perfume composition                                                                            Piney with cocoa-like and                                    of Example XIIIh.                                                                              coffee-like topnotes.                                        Perfume composition                                                                            Piney with valerian-like and                                 of Example XIIIi.                                                                              green topnotes and toasted                                                    almond undertones.                                           Perfume composition                                                                            Piney with jasmine-like                                      of Example XIIIj.                                                                              topnotes.                                                    Perfume composition                                                                            Piney with valerian-like                                     of Example XIIIk.                                                                              and green topnotes.                                          ______________________________________                                    

EXAMPLE XV PERFUMED LIQUID DETERGENT

Concentrated liquid detergents (Lysine salt of n-dodecylbenzene sulfonicacid as more specifically described in U.S. Pat. No. 3,948,818 issued onApr. 6, 1976 the specification for which is incorporated herein) witharomas as set forth in Table I of Example XIV, supra are preparedcontaining 0.10%, 0.15, 0.20%, 0.25%, 0.30% and 0.35% of eachof thesubstances of Table I of Example XIV. They are prepared by adding andhomogeneously admixing the appropriate quantity of one of the substancesof Table I of Example XIV in the liquid detergent. The detergents allpossess excellent aromas as set forth in Table I of Example XIV.

EXAMPLE XVI PREPARATION OF A COLOGNE AND HANDKERCHIEF PERFUME

The substances set forth in Table I of Example XIV are incorporatedseparately into colognes at concentrations of 2.0%, 2.5%, 3.0%, 3.5%,4.0%, 4.5% and 5.0% in 75%, 80%, 85%, and 90% aqueous food grade ethanolsolutions; and into handkerchief perfumes at concentrations of 15%, 20%,25% and 30%, in 80%, 85%, 90% and 95% aqueous food grade ethanolsolutions. Distinctive aromas as set forth in Table I of Example XIV,supra are imparted to the colognes and to the handkerchief perfumecompositions at all levels indicated.

EXAMPLE XVII PREPARATION OF SOAP COMPOSITION

One hundred grams of soap chips (IVORY®, produced by the Procter &Gamble Company, of Cincinnati, Ohio) are admixed with 1 gram of each ofthe substances of Table I of Example XIV, supra. until homogeneouscompositions are obtained. The homogeneous compositions are eachseparated then heated under 3 atmospheres pressure at 180° C. for aperiod of 3 hours and the resulting liquid samples are placed in soapmolds. The resulting soap cake, on cooling, manifest excellentlong-lasting aromas as set forth in Table I of Example XIV, supra.

EXAMPLE XVIII PREPARATION OF SOLID DETERGENT COMPOSITIONS

Detergents are prepared from the following ingredients according toExample I of Canadian Letters Patent 1,007,948 the specification forwhich is incorporated by reference herein:

    ______________________________________                                        Ingredients        Parts by Weight                                            ______________________________________                                        Neodol ® 45-11 (a C.sub.14 --C.sub.15                                                        12                                                         alcohol ethoxylated                                                           with 11 moles of ethylene                                                     oxide)                                                                        Sodium carbonate   55                                                         Sodium citrate     20                                                         Sodium sulfate, water                                                                            q.s.                                                       brighteners                                                                   ______________________________________                                    

This detergent is a phosphate-free detergent. A total of 100 grams ofsaid detergent is admixed separately with 0.10, 0.15, 0.20 and 0.25grams of each of the substances of Table I of Example XIV. Each of thedetergent samples has an excellent aroma as set forth in Table I ofExample XIV.

EXAMPLE XIX DRYER-ADDED FABRIC SOFTENER ARTICLE

Utilizing the procedure of Example I at column 15 of U.S. Pat. No.3,632,396, the specification for which is incorporated by referenceherein, a non-woven cloth substrate useful as a dryer-added fabricsoftening article of manufacture is prepared wherein the substrate, thesubstrate coating and the outer coating and the perfuming material areas follows:

1. A water "dissolvable" paper ("Dissolvo Paper")

2. Adogen 448 (m.p. about 140° F.) as the substrate coating; and

3. An outer coating having the following formulation (m.p. about 150°F.):

57% C₂₀₋₂₂ HAPS

22% isopropyl alcohol

20% antistatic agent

1% of one of the substances of Table I of Example XIV, supra.

Fabric softening compositions containing one of the substances of TableI of Example XIV consist essentially of a substrate having a weight ofabout 3 grams per 100 square inches of substrate coating having a weightof about 1.85 grams per 100 square inches; and an outer coating having aweight of about 1.4 grams per 100 square inches thereby providing atotal aromatized substrate and outer coating weight ratio of about 1:1by weight of the substrate.

Pleasant aromas as set forth in Table I of Example XIV are imparted tothe head space in the dryer on operation thereof using the saiddrier-added fabric softening non-woven fabric.

EXAMPLE XX RASPBERRY FLAVOR FORMULATION

The following basic raspberry flavor formulation is produced:

    ______________________________________                                        Ingredients         Parts by Weight                                           ______________________________________                                        Vanillin             2.0                                                      Maltol               5.0                                                      Parahydroxybenzylacetone                                                                           5.0                                                      Alpha-ionone (10% in propylene                                                                     2.0                                                      glycol)                                                                       Ethyl butyrate       6.0                                                      Ethyl acetate       16.0                                                      Dimethyl sulfide     1.0                                                      Isobutyl acetate    13.0                                                      Acetic acid         10.0                                                      Acetaldehyde        10.0                                                      Propylene glycol    930.0                                                                         1000.0                                                    ______________________________________                                    

The compound having the structure: ##STR258## is added to half of theabove formulation at the rate of 0.2%.

The formulation with the compound having the structure: ##STR259##prepared according to Example II is compared with the formulationwithout that compound at the rate of 0.01% (100 ppm) in water andevaluated by a bench panel consisting of five members, none of whom isassociated with the inventors on the instant application and each ofwhom is independent of the assignee of the instant application.

The flavor containing the compound having the structure: ##STR260## isfound to have a substantially more pleasant and better raspberry aroma.It is the unanimous opinion of the bench panel that the chemical havingthe structure: ##STR261## rounds out the flavor and contributes to avery natural fresh aroma and taste found in fresh raspberries whereby araspberry kernel character is imparted in both aroma and taste.Accordingly, the flavor with the addition of the compound having thestructure: ##STR262## is considered substantially better than the flavorwithout the compound having the structure: ##STR263##

EXAMPLE XXI FLAVOR COMPOSITION

The following basic walnut flavor formulation is prepared as follows:

    ______________________________________                                        Ingredients           Parts by Weight                                         ______________________________________                                        Ethyl-2-methyl butyrate                                                                             10.0                                                    Vanillin              40.0                                                    Butyl valerate        40.0                                                    2,3-Diethyl pyrazine   5.0                                                    Methyl cyclopentenolone                                                                             80.0                                                    Benzaldehyde          60.0                                                    Valerian oil Indian    0.5                                                    (1% in 95% aqueous ethanol alcohol)                                           Propylene glycol      764.5                                                   ______________________________________                                    

The resulting flavor is split into four portions. To each of the firstthree portions, separately, the following materials are added:

(i) The compound having the structure: ##STR264## produced according toExample VII; (ii) The compound having the structure: ##STR265## preparedaccording to Example VIII; and (iii) The compound having the structure:##STR266## prepared according to Example X.

To the fourth portion nothing is added.

The compounds of Examples VII, VIII and X are added at the rates of 1.5%each.

The formulations with the alkyl substituted and unsubstitutedpara-carboalkoxy cyclohexanones of our invention as set forth, supra arecompared to the formulation which does not have such a alkyl substitutedand unsubstituted para-carboalkoxy cyclohexanones. The formulationcontaining the alkyl substituted and unsubstituted para-carboalkoxycyclohexanones are evaluated by an independent bench panel of flavorpanelist who are not associated with the inventors or with the assigneeof the instant application as follows:

(i) A woody, balsamic, fresh walnut kernel and walnut skin-like tastewith excellent caramel-like, maple sugar-like nuances;

(ii) A roasted walnut-like aroma and taste with maple/hazel-nut nuances;and

(iii) A natural walnut aroma and taste with fresh almond aroma and tastenuances.

The flavors that have added to them the above-named alkyl substitutedand unsubstituted para-carboalkoxy cyclohexanones of our invention areunanimously preferred by the group of flavor panelist over the flavornot containing said alkyl substituted and unsubstituted para-carboalkoxycyclohexanones.

EXAMPLE XXII BEVERAGE

The addition of one of the alkyl substituted and unsubstitutedpara-carboalkoxy cyclohexanones of our invention set forth belowprepared according to the examples as set forth below, at the rate of 7ppm to a commercial cola beverage gives the beverage a fullerlong-lasting natural like taste having the following flavor nuances:

    ______________________________________                                                           Aroma and Taste                                            ______________________________________                                         ##STR267##          A cola beverage aroma  and taste with                                         tart  unripened lime aroma and taste nuances.             ##STR268##          A fresh natural cola aroma and taste                                          with aesthetically pleasing bitter lemony aroma and                           taste nuances.                                            ##STR269##          A sweetened cola bev- erage taste with maple                                  sugar-like nuances.                                       ##STR270##          An interesting cola beverage aroma and taste with                             cocoa and coffee-like nuances.                           ______________________________________                                    

In all cases a bench panel having five members not associated with theinventorship entity of the instant application or the assignee of theinstant application unanimously is of the opinion that the colabeverages with the above-mentioned alkyl substituted and unsubstitutedpara-carboalkoxy cyclohexanones of our invention are preferred over thecola beverages without those alkyl substituted and unsubstitutedpara-carboalkoxy cyclohexanones of our invention.

EXAMPLE XXIII FLAVORED PEANUT BUTTER

To a standard peanut butter mix (PLANTERS®) is admixed at the rate of 4ppm one of the following materials:

(i) The compound having the structure: ##STR271## produced according toExample X; (ii) The compound having the structure: ##STR272## preparedaccording to Example VI; (iii) The compound having the structure:##STR273## produced according to Example VIII.

To a fourth sample nothing is added.

The compound having the structure: ##STR274## prepared according toExample X imparts to this peanut butter a fresh almond aroma and tasteat the level of 10 ppm in addition to the pleasant peanut-like nuances.

The compound having the structure: ##STR275## prepared according toExample VIII added at the rate of 5 ppm imparts to this peanut butter apleasant maple/hazel nut aroma and taste profile at 5 ppm causing it tobe more aesthetically pleasing.

The compound having the structure: ##STR276## prepared according toExample VI imparts a fresh peanut aroma and taste profile ("newly pickedpeanuts") to this peanut butter.

A bench panel of five members not associated with the inventorshipentity of the instant application and not associated with the assigneeof the instant application, unanimously prefers the peanut buttercontaining the alkyl substituted and unsubstituted para-carboalkoxycyclohexanones of our invention as set forth, supra to the peanutbutters not containing the alkyl substituted and unsubstitutedpara-carboalkoxy cyclohexanones of our invention.

What is claimed is:
 1. The process for preparing the compound having thestructure: ##STR277## wherein R₁ " represents C₁ -C₆ alkyl and R₂ isselected from the group consisting of ethyl and methyl comprising thestep of reacting the compound having the structure: ##STR278## withhydrogen in the presence of a palladium catalyst at temperatures in therange of from about 130° C. up to about 170° C. and pressures in therange of from about 40 psig up to about 100 psig in order to create amixture of compounds having the structures: ##STR279## and separating bymeans of fractional distillation the compound having the structure:##STR280## from the compound having the structure: ##STR281## and thenreacting the compound having the structure: ##STR282## with an aldehydedefined according to the structure: ##STR283## in the presence ofhydrogen chloride gas at a temperature in the range of from about -10°C. up to about +10° C. and in the presence of a solvent inert to thereactants or products of reaction, the ratio of aldehyde having thestructure: ##STR284## to ketone having the structure: ##STR285## varyingfrom about 0.5:1.5 up to about 1.5:05, thereby forming the compoundhaving the structure: ##STR286## and then reacting the compound havingthe structure: ##STR287## with hydrogen in the presence of apalladium-on-carbon catalyst or a palladium-on-calcium carbonatecatalyst at a pressure in the range of 35 psig up to 150 psig in thepresence of an inert solvent in order to form the compound having thestructure: ##STR288## and then recovering the compound having thestructure: ##STR289## by means of fractional distillation.